Printing with onium dyestuffs and buffer mixtures



Patented June 3, 1952 Pairwise WITH. oNmMnYEsrUErs AND BUF E XT RE 110m Chadderton and Raymondi'lihornton, Blaclg ley, Manchester, England, assignors telmperial, Chemical Industries Limited, .a corporation. of

Great firitain Nollrayqing. Application June- 30, 1948, Serial Massage. In Great Britain l uly lllf,fl;9 7

i vee en i i- 3%? E- PlQll i P3 w .7 ari ew r -te q ss for local co urationoj textile. materials and paper with dyestuffs which. contain. quaternary or ternary l -sm le InBritishspecificationsNos. 576,234, 57 6,270 and 587,636 processesare described for themanufactureof certain .dyestufisusefulfor. the dyeing of textile. materials which. contain quaternary ammoniurn, ternary sulphonium or 'is othiouronium salt groups, attached through methylene linkages to aromatic nuclei. Also'in the specification of co-pending U. S. application S. N. 758,468, filed July 1, 1947 now issued as U. S. PatentNo. 544,825.- of' March 13; 1951, a: process is describedsfor. making-dyestuffs. of the anthraquinone series-.andzrelated'polycyclic. ketone types, for example; dyestufis-ofthe. acedianthranone, dibenZ- anthrone; isodihenzanthrone, indanthrone, and

perylene tetracarboxy,-;di1(pheny1imide) series which. contain similarsalti groups attached through methylene linkages toaromatic nuclei.

We have now found that dyestufi's of the above kind which we call "-onium dyestuffs are of exceptional value for application tofibrous materials, particularly textile materials and paper, by printing and other local colouration processes.

We have also found'thatsuch dyestuffs can be applied by padding-processesgandjthat'when textilematerialor paper whichhas; previously been printed with resists, is padded with a solution of "onium" dyestuff, thedyfistwu fu is applied to the nresisiediportionspi the.- material orpaper and valuable: local.- cclcuration .eiffectsare obtained,

According toourginvention therefore we provide a process for the productioni of coloured patismedsfieqi ceramic ma eri s oripaper which comprises: applying locally to thetextile material an Pan -dye t s sw mmin quaternary ammoniuin; ternaryv sulphonium or, isothiouronium salt iiQlPfi- The onium. dyestuffs may beapplied locally brewer e .9 ra ti ut' h m important method of application isby printing by the hand block, screen or roller techniques.

The onium dyestufis can be printed alongside other types of dyestuffs used for printing andthisformsa further-feature ofjour invention.

The-"Onium'Y-" dyestuiTs: may be applied in aqueoussolution or in a printingpaste' inthe presence of 'a' weaklyacidic substance and then the textile material' orpapertreated with an alkaline substance before, during or after the application of the dyestuff."

The onium dyestuffs :a-re however-preferably from a Weakly: acid to1a Weakly alkaline state,

which change; facilitates, the; fixation OffthQQYfistuffs. on-the-teXtile-o paper,

As suitable Weak acids there; may bementioned for example, formic, acetic; mono diandtrichloroacetic, diglycollic, citric,- lactic,, tartaric, maleicand. oxaiic-acids, and as: a u a le ad salt theremay bementionedsodium dihydrogen phosphate.

As suitablelalkaline-salts of wealgacids; ,there may be; mentioned sodium salts; of-' acetic; borie and trichloroacetic; acids; trisodiumnphosrphate and disodium hydrogen phosphate.

The choice of particular. acidsor salts; Willyhfi determined by the conditionszto bQuse J n: th printing processes. Thusfor example; Whenthe -oniuml dyestufif is to .be-printed'alongside avat dyestufi it is preferredito useanon-vmat le-acifl for example-lactic acid, inorder-tozavdid.reduiring the printing strengthpf: the vat: dyestuff.

The -oniurnl"dyestuils are exceptionally valuable fonusein printing processes since by'their use it is possible to obtain, the. high fastness properties: of: the vat and" azoic. dyestuffs-with much simpler methods of operationthanthose requiredfor printing with vat and azoio dyestuffs. Furthermore it 'is possible by theuse of the onium dyestuffs to supplement existingranges of printin dyestuffscandto fill in the fastness and shade gaps in the'existing ranges of dyestuffsusedforbrinting, notably theyat' andanoic ranges. The blue and green shades obtainable from onium dyestuffsfierived from phthalosyaninesare of particular interest-for. these purposes.

The onium dyestuffs may be-mixed' with one another 'in the same solution or'printing paste and-they may-be mixed with suitable dyestuffs of bther types 'For example, attractive green shades can bebtainedbymixingablue onium" dyestufi with a yellow-'dyestuifof a different range, for examplea yellow-Water soluble o r dispe sd, cellulose acetate sill; dyestuli The-opium dyestuffs inthe form of printing pastes may be printed"alongsidev one-or more printing pastes containing a vat dyestufi, a mu;- ture of aniline and an oxidising agent suitable for yielding aniline black, a mixture of'anarylamide of 2t 3 hydroxynaphthoic acid and a stabilised form of adiazo compound... or a leugq slll: phuricesier d r ya ye o a a yestufi Also the onium dyestuif may be printed in admixture with and/or alongside a diazo compound or a stabilised form of a diazo compound on textile material which has previously been padded in an alkaline solution of an arylamide of 2 :3-hydroxynaphthoic acid.

Among the other many combinations by which novel and useful effects can be obtained there may be mentioned:

(1) Padding with an alkaline solution of a 2:3- hydroxynaphthoic arylamide, printing in succession with (a) an onium dyestufl, (b) an acidic paste containing a stabilised diazo compound, (c) an acidic white resist and subsequently padding with a solution of a stabilised form of a second diazo compound, which diazo compound does not couple under acidic conditions for example Brentamine Fast Blue VB salt.

(2) Printing in succession with (a) an onium dyestuff, (b) a stabilised azoic combination and (c) a zinc oxide white resist, acid steaming, and then padding with an aniline black mixture and developing.

(3) Printing in succession with (a) an onium dyestuif, (b) a zinc oxide while resist, (c) a vat dyestufi and zinc oxide and then padding with a solution of a leuco sulphuric ester derivative of a vat dyestuif and developing.

(4) Printing with a white resist and then with one or more pastes containing a stabilised diazo compound and a wax thickening mixture, on a textile material which has previously been padded with an alkaline solution of a 2:3-hydroxynaphthoic arylamide and dried, drying and padding with an onium dyestufl solution.

(5) Printing with a paste containing a stabilised azoic combination and a parafiin wax emulsion, acid steaming, drying, and then padding with a solution of an onium" dyestuff.

(6) Printing with a paste containing a vat dyestuil, a wax resist, an alkali and a. reducing agent, drying and then padding with a solution of an onium dyestuff.

The textile materials which may be coloured locally by the process of our invention include cotton, viscose rayon, cuprammonium rayon, natural silk, acetate rayon, nylon, chlorinated wool, linen and jute.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 The printing paste is prepared as follows: A solution of 0.5 part of the dyestufi obtained by reacting copper tri- (chloromethyl) phthalocyanine with tetramethylthiourea and 5.0 parts of glacial acetic acid in 17.0 parts of water is added with stirring to The above printing paste is printed on cotton material. The print is dried and developed by steaming for 5 minutes at 100 C. and is then finished by rinsing in cold water, soaping at the described in British specifications Nos. 576,234,

576,270 and 587,636 and in U. S. application S. N. 758,468, filed July 1, 1947, now U. S. Patent No. 2,544,825.

Example 2 A printing paste is prepared as follows: A solution of V 0.75 part of the dyestufl obtained by reacting bis (chloromethyl)acedianthrone with pyridine and parts of glacial acetic acid in parts of water, is added with stirring to parts of tragacanth thickening (made by boiling together 8 parts of gum tragacanth in 92 parts of water) parts of a solution of sodium acetate (made by dissolving 5 parts of hydrated sodium acetate in 7.5 parts of water) is then added to the thickened dyestuff paste. 4.75 parts of a solution of sodium m-nitrobenzene sulphonate (made by dissolving 0.1 part of sodium m-nitrobenzene sulphonate in 4.65 part of water) is added.

Example 3 A printing paste is prepared as follows: A solution of 2.0 parts of the dyestuff obtained by reacting (ii-(chloromethyl) -4:4' di-(6 methylbenzthiazyl-Z) azobenzene with pyridine, and

5.0 parts of glacial acetic acid in 10.5 parts of water is added with stirring to 65.0 parts of gum tragacanth dispersion (made by boiling 8 parts of gum tragacanth with 92 parts of water) 12.5 parts of a solution of sodium acetate (made by dissolving 5 parts of hydrated sodium acetate in 7.5 parts of water) is then added to the thickened dyestuif paste.

5.0 parts of a solution of sodium chromate solution (made by dissolving 0.2 part of hydrated sodium chromate in 4.8 parts of water) is added.

The above printing paste is printed on cuprammonium rayon material. The print is dried and developed by steaming for 40 minutes at 100 C. and then finished off by rinsing in water and soaping at 50 C. for 10 minutes. It is then rinsed and dried.

The print obtained is a bright yellow shade of good fastness properties.

remain A printing'paste is'preparedasitollows .Asolution of 0.75 part of the dyestufinbtained by reacting copper tri-(chloromethyl) phthalocyamine .with .tetramethyl thiourea, and

35.0 i'par'ts ofglacialacetie-acidin 1635. parts. of .water .is added :with stirring to 565.0 parts oigum tragacanthiithickeningC(made by boiling together 8 parts of gum tragacanth withQZ partS of-Water) 12.5 :parts of a solution '-of sodium -.acetate .imade by dissolving 15 parts of; hydrated .-:sodium acetateiin' 7.5,parts of -water) is then added :to the thickened gdyestuff paste.

Ann's- The above printing paste is printed on acetate rayon material. The print is dried and developed by steaming for 20 minutes at 100 C. It is finished ofi by rinsing in cold water, soaping for 5 minutes at 40 C. in 0.2% soap solution and finally rinsing and drying.

- The print so obtained is a bright greenish blue shade of good fastness properties.

Example 5 A printing paste (A) is prepared as follows: A solution of 1.5 parts of Solacet Fast Yellow GS in 33.5 parts of water is added with stirring to 65.0 parts of gum tragacanth thickening (made by boiling together 8 parts of gum tragacanth and 92 parts of water) A printing paste (B) is prepared exactly as described in Example 4. I

A printing paste is now prepared by mixing equal parts of A and B and this paste is printed on nylon textile material. The print is dried and developed by steaming for 30 minutes at 100 C. The print is then finished off by rinsing in cold water, soaping for 5 minutes at 40 C. rinsing and drying.

The print so obtained is a bright green shade of good fastness properties.

Example 6 B 0 (parts) (parts) Caledon Purple 4RP 150 Paste Fine 8 Caledon Grey 3BPS Paste 1 Thin British Gum thickening... 12 19 Vat Colour thickening 80 80 Total 100 100 The thin British gum thickening is prepared by boiling 4 parts of British gum with 7.5 parts of water.

ii. tithe "eeolour :thickenlng .iris imifimd ins fI'he printing pastes .13. 111 42110 :are gnrinte successively on cotton materlailufiried, ideiieloped by steaming for-five. minutesat "100 C. pmdise-d in, a;-c01'd1s0111t10 of 025% p assiumdichroma and 0.5% acetic acid, rinsed; soap'edii01'11l0ii111ihutes at ..l.00.. C. ,in 0.2% soap s0lution',"'rinsed"and finallylfiried.

The resulting printis a" three colour patterned effect of purple, grey and bright turquoise blue shades of good fastness properties.

Example 7 A printing paste (A) is prepared according to the directions given for paste A in Example 6.

A printing paste (B) is prepared from the vat dyestufi Caledon Printing Blue RNS paste as follows:

Parts Caledon Printing Blue RNS paste 10 Thin British gum thickening (made as described in Example 6) 10 Vat colour thickening (made as described in Example 6) A printing paste (C) is prepared as follows: A dispersion of Parts Brentogen Scarlet RS 6.0

In ethyl alcohol 1.5

And water 12.5 is added to Starch tragacanth thickening (prepared The printing pastes A, B and C are printed successively on cotton material. The material is dried, developed by steaming for 5 minutes at 100 C. oxidised in a cold solution of 0.25% potassium dichromate and 0.5% acetic acid, rinsed, soaped for 10 minutes at 100 C. in 0.2% soap solution, rinsed and dried.

The resulting print is a three colour patterned efiect of scarlet, royal blue and bright turquoise blue shades of good fastness properties.

We claim:

1. A process for the production of colored patterned effects on absorptive fibrous materials by local application of a dyestuff containing a water-solubilizing group selected from the class consisting of quaternary ammonium, tertiary sulionium and i'sothiouronium salt groups, which comprises applying said dyestufi locally to said material in the presence of a buffered composition comprising a mixture of a member selected from the group consisting of weak acids and acid salts and an alkaline salt of a weak acid, which composition on heating changes from a weakly acid to a weakly alkaline state, and thereafter heating said material to convert said composition to its alkaline state and fix said dyestufl'.

2. The process of claim 1, wherein said bufiered composition comprises a mixture of acetic acid and sodium acetate.

3. The process of claim 1, wherein the fibrous material is a textile material and the dyestufi is 15 8 REFERENCES CITED The following references are of record in the file 01' this patent:

UNITED STATES PATENTS Number Name Date 2,120,741 Graenacher June 14, 1938 2,277,628 Bradbrook Mar. 24, 1942 2,290,906 Coffey July 28, 1942 2,464,806 Haddock Mar. 22, 1949 FOREIGN PATENTS Number Country Date 215,947 Switzerland Nov. 1, 1941 525,237 Great Britain Aug. 23, 1940 576,234 Great Britain Mar. 25, 1946 576,270 Great Britain Mar. 26, 1946 587,636 Great Britain May 1, 1947 

1. A PROCESS FOR THE PRODUCTION OF COLORED PATTERNED EFFECTS ON ABSORPTIVE FIBROUS MATERIALS BY LOCAL APPLICATION OF A DYESTUFF CONTAINING A WATER-SOLUBILIZING GROUP SELECTED FROM THE CLASS CONSISTING OF QUATERNARY AMMONIUM, TERTIARY SULFONIUM AND ISOTHIOURONIUM SALT GROUPS, WHICH COMPRISES APPLYING SAID DYESTUFF LOCALLY TO SAID MATERIAL IN THE PRESENCE OF A BUFFERED COMPOSITION COMPRISING A MIXTURE OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF WEAK ACIDS AND ACID SALTS AND AN ALKALINE SALT OF A WEAK ACID, WHICH COMPOSITION ON HEATING CHANGES FROM A WEAKLY ACID TO A WEAKLY ALKALINE STATE, AND THEREAFTER HEATING SAID MATERIAL TO CONVERT SAID COMPOSITION TO ITS ALKALINE STATE AND FIX SAID DYESTUFF. 